This invention relates to a silver halide photographic element containing a phenolic cyan dye-forming coupler bearing a substituted or unsubstituted vinyl carbonamido group in the 2-position and a carbonamido substituent bearing a sulfone, sulfoxide or sulfonamide group in the 5-position.
In silver halide based color photography, a typical photographic element contains multiple layers of light-sensitive photographic silver halide emulsions coated on a support with one or more of these layers being spectrally sensitized to each of blue light, green light and red light. The blue, green, and red light-sensitive layers typically contain yellow, magenta, and cyan dye-forming couplers, respectively. After exposure to light, color development is accomplished by immersing the exposed material in an aqueous alkali solution containing an aromatic primary amine color-developing agent. The dye-forming couplers are selected so as to react with the oxidized color developing agent to provide yellow, magenta and cyan dyes in the so called subtractive color process to reproduce their complementary colors, blue, green and red as in the original image.
The important features for selecting the dye-forming coupler include, efficient reaction with oxidized color developing agent, thus minimizing the necessary amounts of coupler and silver halide in the photographic element; the formation of dyes with hues appropriate for the photographic use of interest, for color photographic paper applications this requires that dyes have low unwanted side absorption leading to good color reproduction in the photographic print; minimization of image dye loss contributing to improved image permanence under both ambient illumination and conventional storage conditions; and in addition the selected dye-forming coupler must exhibit good solubility in coupler solvents, provide good dispersibility in gelatin and remain stable during handling and manipulation for maximum efficiency in manufacturing processes.
In recent years, a great deal of study has been conducted to improve dye-forming couplers for silver halide photosensitive materials in terms of improved color reproducibility and image dye stability. However, further improvements are needed, particularly in the area of cyan couplers. In general, cyan dyes are formed from naphthols and phenols as described, for example, in U.S. Pat. Nos. 2,367,351, 2,423,730, 2,474,293, 2,772,161, 2,772,162, 2,895,826, 2,920,961, 3,002,836, 3,466,622, 3,476,563, 3,552,962, 3,758,308, 3,779,763, 3,839,044, 3,880,661, 3,998,642, 4,333,999, 4,990,436, 4,960,685, and 5,476,757; in French patents 1,478,188 and 1,479,043; and in British patent 2,070,000. These types of couplers can be used either by being incorporated in the photographic silver halide emulsion layers or externally in the processing baths. In the former case the couplers must have ballast substituents built into the molecule to prevent the couplers from migrating from one layer into another. Although these couplers have been used extensively in color photographic film and paper products, the dyes derived from them still suffer from poor stability to heat, humidity or light, low coupling efficiency or optical density, and in particular from undesirable blue and green absorptions which cause considerable reduction in color reproduction and color saturation.
Cyan couplers which have been recently proposed to overcome some of these problems are 2,5-diacylaminophenols containing a sulfone, sulfonamido or sulfate moiety in the ballasts at the 5-position, as disclosed in U.S. Pat. Nos. 4,609,619, 4,775,616, 4,849,328, 5,008,180, 5,045,442, and 5,183,729; and Japanese patent applications JP02035450 A2, JP01253742 A2, JP04163448 A2, JP04212152 A2, and JP05204110 A2. Even though cyan image dyes formed from these couplers allege in various instances improved stability to heat and humidity, enhanced optical density and resistance to reduction by ferrous ions in the bleach bath, the dye absorption maxima (xcexmax) are too hypsochromically shifted (that is, shifted to the blue end of the visible spectrum) and the absorption spectra are too broad with considerable amounts of undesirable blue and green absorptions and often lack sufficient stability toward light fading. Thus, these couplers are not acceptable for use in color papers and print applications.
The hue of a dye is a function of both the shape and the position of its spectral absorption band. Traditionally, the cyan dyes used in color photographic papers have had nearly synnetrical absorption bands centered in the region of 620 to 680 nm, typically 630 to 660 nm. Such dyes have rather large amounts of unwanted absorption in the green and blue regions of the spectrum.
More desirable would be a dye whose absorption band is asymmetrical in nature and biased towards the green region, that is, with a steep slope on the short wavelength side. The half-bandwidth on the short side of the curve, also called the left half-bandwidth or LBW, is desirably narrowed. Such a dye would suitably peak at a shorter wavelength than a dye with symmetrical absorption band, but the exact position of the desired peak depends on several factors including the degree of asymmetry and the shapes and positions of the absorption bands of the magenta and yellow dyes with which it is associated.
Recently, Lau et al., in U.S. Pat. No. 5,686,235, and Begley et al., in U.S. Pat. Nos. 6,387,606, 6,251,575, 6,207,363, 6,201,125, 6,197,492, 6,197,491, 6,197,490, 6,197,489, 6,194,132, 6,190,850, 6,180,331, 6,180,328, and 6,132,947 describe particular classes of cyan dye-forming couplers that have been shown to improve thermal stability and hue, particularly, with decreased absorption in side bands and absorption bands that are asymmetrical in nature. The couplers disclosed as suitable contain a sulfone, sulfoxide or sulfonamide groups bonded to the 2 or 3-positions of a carbonamido group at the 5-position of the phenolic ring and contain a carbocyclic or heterocyclic containing carbonamido group in the 2-position of the phenolic ring. Other related patents are U.S. Pat. Nos. 5,047,314, 5,047,315, 5,057,408, 5,162,197, and 5,789,146.
Although the couplers of Lau et al. and Begley et al. provide advantageous spectra, it is desirable to discover alternative phenolic structures that will accomplish the same result and that may provide other desirable features. Particularly desirable features of phenolic couplers in photographic systems are those of increased coupler solubility, lower crystallinity and lower melting points. Such features allow for the easier incorporation of the coupler into the photographic element and lower the propensity of the coupler to crystallize once incorporated into the element. Honan et al., U.S. Pat. Nos. 6,132,947, 6,190,851 and 6,110,658, describes methods and procedures to overcome the incorporation of less soluble couplers into photographic elements. However, such methods and procedures severely limit the location and types of addenda such as stabilizer and coupler solvent which can be used in film building. Chemical variations may enable advances in the ability to better select the desired curve shape, wavelength of maximum absorption, coupler solubility, lower crystallinity, lower melting points and other properties such as coupler and dye light and dark stability, reactivity etc.
Japanese published application 59-111,645 suggests certain phenolic couplers having an xcex1-sulfonyl substituent in a 5-carbonamido substituent that forms a dye having a maximum absorption at xe2x80x9cabout 660 nmxe2x80x9d with examples of 657-660 nm. It appears that the spectral curves of the disclosed dyes exhibit the usual broad absorption band but that the curve has been shifted to the long wavelength side in order to reduce the unwanted absorption on the short wavelength side. The disclosed compounds do not provide the desired narrow LBW and shorter wavelength of maximum absorption.
In spite of the ongoing efforts to discover soluble, low crystallinity couplers that produce dyes having advantageous absorption properties, such couplers, even if obtained, will have limited utility if the formed dyes are not sufficiently stable.
The problem to be solved is to provide an alternative photographic element, compound, and process, employing a cyan dye-forming phenolic coupler soluble in photographic coupler solvents with low crystallinity, which forms a dye having a narrowed LBW and corresponding lower unwanted side absorptions.
The invention provides a photographic element comprising a light-sensitive silver halide emulsion layer having associated therewith a cyan xe2x80x9cNB couplerxe2x80x9d having the formula: 
wherein:
the term xe2x80x9cNB couplerxe2x80x9d represents a coupler of formula (I) that 5 forms a dye with the developer 4-amino-3-methyl-N-ethyl-N-(2-methanesulfonamidoethyl) aniline sesquisulfate hydrate for which the left bandwidth (LBW) using spin-coating is at least Sni less than that of the same dye in solution form;
V is a sulfone, sulfoxide or sulfonamide-containing group;
Y is H or a coupling-off group;
each Z1, Z2, Z3 and Z* are an independently selected substituent group where p is independently 0 to 2;
provided that Z1 and Z2 or Z2 and Z3 can join to form a ring;
provided further that Z1 and Z2 do not join to form an aromatic or heterocyclic ring; and
provided further that the combined sum of the aliphatic carbon atoms in V, all Z1, Z2, Z3 and all Z* is at least 8.
The invention also provides a coupler of formula (I) and an imaging method employing the element. The cyan xe2x80x9cNB couplerxe2x80x9d of the invention exhibits advantageous solubility in photographic coupler solvents, and the dye formed in the element exhibits an advantageous dye hue in having a reduced level of unwanted absorption on the short wavelength side of the spectrum and increased stability.